JP5811257B2 - Water-based emulsion surface treatment agent - Google Patents

Description

  The present invention relates to a water-based emulsion surface treatment agent, particularly a water- and oil-repellent agent and an antifouling agent.

Conventionally, a fluorine-containing water and oil repellent containing a fluorine compound is known. This water / oil repellent exhibits good water / oil repellency when treated on a substrate such as a textile product.
From recent research results [EPA report "PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS" (http://www.epa.gov/opptintr/pfoa/pfoara.pdf)] Concerns about the environmental impact of PFOA (perfluorooctanoic acid), a type of fluoroalkyl compound, have become apparent, and on April 14, 2003, EPA (US Environmental Protection Agency) will strengthen scientific research on PFOA Announced.
Meanwhile, Federal Register (FR Vol.68, No.73 / April 16, 2003 [FRL-2303-8], http://www.epa.gov/opptintr/pfoa/pfoafr.pdf) and EPA Environmental News FOR RELEASE : MONDAY APRIL 14, 2003 EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID (http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf) and EPA OPPT FACT SHEET April 14, 2003 (http: // www. epa.gov/opptintr/pfoa/pfoafacts.pdf) publishes that telomers can produce PFOA by degradation or metabolism (telomers mean long chain fluoroalkyl groups). We also announced that telomers are used in many products such as foam, water- and oil-repellent and antifouling foams, care products, cleaning products, carpets, textiles, paper and leather. Yes. There is concern about the accumulation of fluorine-containing compounds in the environment.
In addition, the fluorine-containing water / oil repellent containing the fluorine-containing polymer is subjected to heat treatment at a high temperature (for example, 100 ° C. or more) after being attached to a substrate such as a textile product in order to exhibit water / oil repellency. Must be given. High energy is required for heat treatment at high temperature.
Furthermore, the fluoropolymer is expensive.

Therefore, it may be desired not to use a fluoropolymer or to reduce the amount of the fluoropolymer.
JP 2006-328624 A is a water repellent comprising a non-fluorine polymer containing a (meth) acrylic acid ester having 12 or more carbon atoms in the ester moiety as a monomer unit, the (meth) acrylic acid ester Discloses a water repellent that is 80 to 100% by mass with respect to the total amount of monomer units constituting the non-fluorine polymer.
However, this water repellent is inferior in water repellency.

JP 2006-328624

  An object of the present invention is to provide a surface treating agent that gives excellent water repellency and preferably does not use a fluorine-containing monomer, particularly a fluoroalkyl group-containing monomer.

The present invention
(1) a polymer having a repeating unit derived from a long-chain (meth) acrylate ester monomer,
(2) Provided is a surfactant containing a surfactant compound having one or both of an amide group and an amino group, and (3) an aqueous emulsion treating agent containing a liquid medium containing water.

Preferred embodiments of the present invention are as follows.
[1]
(1) (a) Formula:
^{_{CH 2 = CA 11 -C (=}} O) -O-A 12
[In the formula, A ¹¹ represents a hydrogen atom or a methyl group;
A ¹² is a linear or branched aliphatic hydrocarbon group having 18 to 30 carbon atoms. ]
A non-fluorine polymer having a repeating unit derived from a long-chain (meth) acrylate ester monomer represented by:
(2) A surface treatment agent which is a water-based emulsion containing a surfactant containing a surfactant compound having one or both of an amide group and an amino group, and (3) a liquid medium containing water.
[2]
The surface treating agent according to [1], wherein the non-fluoropolymer (1) has a repeating unit derived from a (meth) acrylate monomer having a cyclic hydrocarbon group.
[3]
A surface active compound having one or both of an amide group and an amino group has the formula:
^{R 11 -C (= O) (} R 12 -) N- (CH 2) n -N - (- R 13) (- R 14)
[In the formula, each of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is independently the same or different and is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and n is 0 to 10. ]
The surface treatment agent according to [1] or [2], which is a compound represented by the formula:
[4]
Surfactant (2) further comprises one or both of a nonionic surfactant and a cationic surfactant,
The nonionic surfactant is at least one selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides;
The surface treatment according to any one of [1] to [3], wherein the cationic surfactant is at least one selected from the group consisting of amine, amine salt, quaternary ammonium salt, imidazoline and imidazolinium salt. Agent.
[5]
The surface treatment agent according to any one of [1] to [4], wherein the surface treatment agent does not contain a fluoropolymer.
[6]
The surface treatment agent according to any one of [1] to [4], wherein the surface treatment agent contains a fluoropolymer.
[7]
The surface treating agent according to any one of [1] to [6], which is a water / oil repellent or an antifouling agent.
[8]
A method for treating a textile product, comprising treating the textile product with the surface treating agent according to any one of [1] to [7].
[9]
A fiber product treated with the surface treatment agent according to any one of [1] to [7].

Since the treatment agent of the present invention does not use a fluoroalkyl group-containing monomer, there is no concern about accumulation of fluorine-containing compounds in the environment. The treatment agent of the present invention imparts excellent water and oil repellency, particularly water repellency, to the substrate. Furthermore, water repellency is exhibited by low temperature treatment without the need for heat treatment at high temperature.
The treatment agent of the present invention is excellent in water repellency durability (particularly washing durability).
Performance equal to or greater than or equal to that of a processing agent containing only a fluoropolymer containing a fluoroalkyl group-containing monomer as an active ingredient by a processing agent containing only a non-fluorine polymer as an active component (especially the initial Water / oil repellency including water / oil repellency).

In the present invention, the polymer (preferably a non-fluorine polymer) is
(A) having a repeating unit derived from a long-chain (meth) acrylate ester monomer.
The polymer may be a copolymer, and
(B) a repeating unit derived from a short chain (meth) acrylate ester monomer,
(C) having at least one repeating unit selected from the group consisting of repeating units derived from non-fluorine crosslinkable monomers, and (d) repeating units derived from halogenated olefin monomers. May be.
The polymer may have a fluorine atom, but preferably does not have a fluorine atom. That is, the polymer is preferably a non-fluorine polymer.

(A) long chain (meth) acrylate ester monomer long chain (meth) acrylate ester monomer has the formula:
^{_{CH 2 = CA 11 -C (=}} O) -O-A 12
[In the formula, A ¹¹ represents a hydrogen atom or a methyl group;
A ¹² is a linear or branched aliphatic hydrocarbon group having 18 to 30 carbon atoms. ]
It is a compound shown by these.
The long chain (meth) acrylate ester monomer does not have a fluoroalkyl group. The long chain (meth) acrylate ester monomer may contain a fluorine atom, but preferably does not contain a fluorine atom.
A ¹¹ is particularly preferably a methyl group.
A ¹² is a linear or branched hydrocarbon group. The linear or branched hydrocarbon group may in particular be a linear hydrocarbon group. The linear or branched hydrocarbon group has 18 to 30 carbon atoms. The linear or branched hydrocarbon group preferably has 18 to 28 carbon atoms, particularly 18 or 22, and is generally a saturated aliphatic hydrocarbon group, particularly preferably an alkyl group.

Particularly preferred specific examples of the long-chain (meth) acrylate ester monomer are stearyl (meth) acrylate and behenyl (meth) acrylate. Stearyl (meth) acrylate is particularly preferred.
The presence of the long-chain (meth) acrylate ester monomer increases the water repellency and texture imparted by the polymer.

(B) short chain (meth) acrylate ester monomer polymer may have the repeating units derived from short-chain (meth) acrylate ester monomer.
The short chain (meth) acrylate ester monomer has the formula:
^{_{CH 2 = CA 21 -C (=}} O) -O-A 22
[In the formula, A ²¹ represents a hydrogen atom or a methyl group;
A ²² is a linear or branched aliphatic hydrocarbon group having less than 18 carbon atoms. ]
It is preferable that it is a compound shown by these.

The short chain (meth) acrylate ester monomer does not have a fluoroalkyl group. The short chain (meth) acrylate ester monomer may contain a fluorine atom, but preferably does not contain a fluorine atom.
A ²¹ is particularly preferably a methyl group.
A ²² is a linear or branched hydrocarbon group. The linear or branched hydrocarbon group may in particular be a linear hydrocarbon group. The linear or branched hydrocarbon group has 1 to 17 carbon atoms. The linear or branched hydrocarbon group preferably has 1 to 14 carbon atoms, and is generally a saturated aliphatic hydrocarbon group, particularly preferably an alkyl group.

Specific examples of short chain (meth) acrylate ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) ) Acrylate, cetyl (meth) acrylate. Particularly preferred specific examples of the short chain (meth) acrylate ester monomer are lauryl (meth) acrylate and cetyl (meth) acrylate.
The presence of the short chain (meth) acrylate ester monomer improves water repellency. The short chain (meth) acrylate ester monomer can be used for adjusting the film forming property.

(C) a non-fluorinated crosslinking monomer polymer may have the repeating units derived from fluorine-free crosslinkable monomer, or may not possess.
A non-fluorine crosslinkable monomer is a monomer which does not contain a fluorine atom. The non-fluorine crosslinkable monomer may be a compound having at least two reactive groups and / or olefinic carbon-carbon double bonds (preferably (meth) acrylate groups) and not containing fluorine. The non-fluorine crosslinkable monomer is a compound having at least two olefinic carbon-carbon double bonds (preferably a (meth) acrylate group), or at least one olefinic carbon-carbon double bond and at least one It may be a compound having a reactive group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, and the like.

The non-fluorine crosslinkable monomer may be mono (meth) acrylate, di (meth) acrylate or mono (meth) acrylamide having a reactive group. Alternatively, the non-fluorine crosslinkable monomer may be di (meth) acrylate.
One example of a non-fluorine crosslinkable monomer is a vinyl monomer having a hydroxyl group.
Examples of non-fluorine crosslinkable monomers include diacetone (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) ) Acrylate, 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di ( Examples include, but are not limited to, (meth) acrylate.
Due to the presence of the non-fluorine crosslinkable monomer, durability (particularly washing durability) is improved.

(D) Halogenated olefin monomer The halogenated olefin preferably has no fluorine atom.
The halogenated olefin is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. The halogenated olefin is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Preferred examples of halogenated olefins are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide. Vinyl chloride is preferred.
Due to the presence of the halogenated olefin, durability (particularly washing durability) is improved.

(E) Other monomers (e) other than the monomer monomers (a) to (d), for example, non-fluorine non-crosslinkable monomers may be used.
Examples of non-fluorine non-crosslinkable monomers include non-fluorine acrylate monomers having a cyclic hydrocarbon group. The non-fluorine acrylate monomer having a cyclic hydrocarbon group is a monomer containing no fluorine atom. A non-fluorine acrylate monomer does not have a crosslinkable functional group. A non-fluorine acrylate monomer is non-crosslinkable unlike a crosslinkable monomer.

Preferred non-fluorinated acrylate monomers having a cyclic hydrocarbon group have the formula:
_{CH 2 = CA-C (=} O) -O-Q
[In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom);
Q is a cyclic hydrocarbon group. ]
It may be a compound shown by these.

The carbon number of the cyclic hydrocarbon group is 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms. Examples of the cyclic hydrocarbon group include 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms, especially 5 to 12 cyclic aliphatic groups, 6 to 30 carbon atoms, preferably 6 to 20 aromatic hydrocarbon groups, and carbon atoms. 7-30, preferably 7-20 araliphatic hydrocarbon groups.
Examples of the cyclic hydrocarbon group include saturated or unsaturated monocyclic groups, polycyclic groups, and bridged cyclic groups. The cyclic hydrocarbon group is preferably saturated.
The number of carbon atoms of the cyclic hydrocarbon group is particularly preferably 15 or less, for example 10 or less. By setting the number of carbon atoms of the cyclic hydrocarbon group within the above range, strong water repellency can be provided.

  Specific examples of the cyclic hydrocarbon group are a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, and an adamantyl group. The acrylate group is preferably an acrylate group or a methacrylate group, but a methacrylate group is particularly preferable. Specific examples of the monomer having a cyclic hydrocarbon group include cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. , Dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl -2-Adamantyl (meth) acrylate and the like.

  In addition, examples of other monomers include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol ( Meth) acrylates and vinyl alkyl ethers are included. Other monomers are not limited to these examples.

  In the present specification, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acrylamide” means acrylamide or methacrylamide.

  Since the water repellency is increased, each of the monomers is preferably an acrylate ester.

  Each of the monomers (a) to (e) may be a single monomer or a mixture of two or more.

The amount of monomer (a) is 40% by weight or more, preferably 50 parts by weight or more based on the polymer. The amount of the monomer (a) may be 95 parts by weight or less, for example 80 parts by weight or less, or 75 parts by weight or less, or 70 parts by weight or less based on the polymer.
In the polymer, with respect to 100 parts by weight of the monomer (a),
The amount of the repeating unit (b) is 0 to 150 parts by weight, preferably 1 to 40 parts by weight,
The amount of the repeating unit (c) is 0 to 50 parts by weight, preferably 1 to 5 parts by weight,
The amount of the repeating unit (d) is 0 to 100 parts by weight, preferably 1 to 30 parts by weight,
The amount of the repeating unit (e) may be 0 to 100 parts by weight, preferably 1 to 30 parts by weight.

The number average molecular weight (Mn) of the polymer may generally be 1000 to 1000000, for example 5000 to 500000, in particular 3000 to 200000. The number average molecular weight (Mn) of the polymer is generally measured by GPC (gel permeation chromatography).
The polymer may be one kind of polymer or a combination of two or more kinds of polymers.

  In the present invention, a monomer is polymerized to obtain a treating agent composition in which the polymer is dispersed or dissolved in a medium.

The monomer used in the present invention may be as follows.
Monomer (a),
Monomer (a) + (b),
Monomer (a) + (c),
Monomer (a) + (b) + (c),
Monomer (a) + (d),
Monomer (a) + (b) + (d),
Monomer (a) + (c) + (d), or Monomer (a) + (b) + (c) + (d).
In addition to the above, the monomer (e) may be used.

  It is preferable to use a non-fluorine crosslinkable monomer (c). The monomer is a combination of monomer (a) + non-fluorine crosslinkable monomer (c) or monomer (a) + non-fluorine crosslinkable monomer (c) + halogenated olefin monomer ( A combination of d) is preferred. In this combination, the water-repellent washing durability is high.

(2) Surfactant The surfactant comprises a surfactant compound having one or both of an amide group and an amino group, or consists of only a surfactant compound having one or both of an amide group and an amino group. Good. The surface active compound is preferably a surface active compound having both an amide group and an amino group (that is, an amidoamine surfactant).
The surfactant may be composed only of a surfactant compound having one or both of an amide group and an amino group (particularly, an amidoamine surfactant (2-1)). Alternatively, the surfactant is added to a surfactant compound having one or both of an amide group and an amino group (amidoamine surfactant (2-1)),
Another surfactant, for example, at least one surfactant selected from the group consisting of a nonionic surfactant (2-2) and a cationic surfactant (2-3) may be contained. Examples of other surfactants include amine surfactants having an oxyalkylene group, amine oxide surfactants, and amphoteric surfactants. It is preferable that the surfactant does not contain an anionic surfactant.

(2-1) Amidoamine surfactant The amidoamine surfactant is a compound having an amide group and an amino group.
Amidoamine surfactants have the formula:
^{R 11 -C (= O) (} R 12 -) N- (CH 2) n -N - (- R 13) (- R 14)
[In the formula, each of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is independently the same or different and is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms;
n is 0-10. ]
It is preferable that it is a compound shown by these.
R ¹¹ is preferably an alkyl group or an alkenyl group. R ¹¹ may have 8 to 30, for example, 12 to 24 carbon atoms. R ¹² , R ¹³ and R ¹⁴ are preferably a hydrogen atom or an alkyl group. R ¹² , R ¹³ and R ¹⁴ preferably have 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms. n is 0-10, for example 1-10, in particular 2-5.

  Specific examples of amidoamine surfactants include isostearic acid diethylaminoethylamide, oleic acid dimethylaminoethylamide, oleic acid dimethylaminopropylamide, oleic acid diethylaminoethylamide, oleic acid diethylaminopropylamide, stearic acid diethylaminoethylamide, stearic acid Diethylaminopropylamide, stearic acid dibutylaminoethylamide, stearic acid dibutylaminopropylamide, stearic acid dipropylaminopropylamide, stearic acid dipropylaminoethylamide, stearic acid dimethylaminoethylamide, stearic acid dimethylaminopropylamide, palmitic acid Diethylaminoethylamide, palmitic acid diethylaminopropylamide, palmitic acid Methylaminoethyl amide, palmitic acid dimethylaminopropylamide, behenic acid diethylaminoethylamide, behenic acid diethylaminopropylamide, dimethylaminopropyl amides behenic acid.

  The amidoamine surfactant may be a salt, such as an acid salt or a quaternary ammonium salt. In the salt, the cationic group is the nitrogen atom of the amino group, and the anionic group varies. Examples of the anionic group include a halogen ion, a sulfate ion, a carboxylate ion having 1 to 4 carbon atoms which may be substituted with a hydroxyl group, or an alkyl sulfate ion having 1 to 4 carbon atoms.

Acid salts are obtained by neutralizing amidoamines with acids, such as inorganic acids and / or organic acids. Examples of inorganic acids include hydrochloric acid, sulfuric acid, and phosphoric acid. Organic acids include short-chain monocarboxylic acids such as acetic acid and propionic acid; long-chain monocarboxylic acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid and erucic acid; malonic acid and succinic acid Dicarboxylic acids such as glutaric acid, adipic acid, maleic acid, fumaric acid, and phthalic acid; hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxyacrylic acid, glyceric acid, malic acid, tartaric acid, and citric acid; poly such as polyglutamic acid Carboxylic acids; acidic amino acids such as glutamic acid and aspartic acid; alkyl sulfates, alkyl sulfonates, alkyl phosphates and the like. Among these, inorganic acids, short-chain monocarboxylic acids, dicarboxylic acids, hydroxycarboxylic acids, acidic amino acids are generally used, and hydrochloric acid, sulfuric acid, acetic acid, succinic acid, glycolic acid, lactic acid, malic acid, citric acid Glutamic acid is particularly used.
Quaternary ammonium salts can be obtained by quaternizing amidoamines.

  Amidoamine surfactants may be nonionic or ionic (cationic), but are preferably nonionic. In the case of nonionic, it is preferable to add an ionic compound such as an acid to ionize it.

(2-2) Nonionic surfactant Examples of the nonionic surfactant include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides.
Examples of the ether are compounds having an oxyalkylene group (preferably a polyoxyethylene group).
Examples of esters are alcohol and fatty acid esters. Examples of the alcohol are 1 to 6 (especially 2 to 5) carbon atoms having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, in particular 5 to 30 carbon atoms.
An example of the ester ether is a compound obtained by adding an alkylene oxide (particularly, ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of the alcohol are 1 to 6 (especially 2 to 5) carbon atoms having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, in particular 5 to 30 carbon atoms.
Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or dialkanolamino. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, in particular 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms having 1 to 3 amino groups and 1 to 5 hydroxyl groups.
The polyhydric alcohol may be a divalent to pentavalent alcohol having 3 to 30 carbon atoms.
The amine oxide may be an oxide of an amine (secondary amine or preferably tertiary amine) (for example having 5 to 50 carbon atoms).

The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The alkylene group in the oxyalkylene group preferably has 2 to 10 carbon atoms. In general, the number of oxyalkylene groups in the molecule of the nonionic surfactant is preferably 2 to 100.
The nonionic surfactant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides, and is preferably a nonionic surfactant having an oxyalkylene group.

Nonionic surfactants are alkylene oxide adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, linear and / or branched fatty acids (saturated and / or unsaturated). Polyalkylene glycol ester, polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), alkylene oxide adduct of acetylene glycol, and the like. Among these, the structures of the alkylene oxide addition moiety and the polyalkylene glycol moiety are polyoxyethylene (POE) or polyoxypropylene (POP) or POE / POP copolymer (random copolymer or block copolymer) Is preferred).
The nonionic surfactant preferably has a structure that does not contain an aromatic group because of environmental problems (biodegradability, environmental hormones, etc.).

Nonionic surfactants have the formula:
^{_{R 1 O- (CH 2 CH 2}} O) p - (R 2 O) q -R 3
[Wherein R ¹ is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an acyl group,
Each of R ² is independently the same or different and is an alkylene group having 3 or more carbon atoms (for example, 3 to 10),
R ³ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms,
p is a number of 2 or more,
q is 0 or a number of 1 or more. ]
It may be a compound shown by these.
R ¹ preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. Preferable specific examples of R ¹ include a lauryl group, a tridecyl group, and an oleyl group.
Examples of R ² are a propylene group and a butylene group.
In the nonionic surfactant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, — (R ² O) _q — may form a polyoxyalkylene chain.

The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly, a polyoxyalkylene chain) in the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, among which an oxypropylene chain is preferable.
Preferred nonionic surfactants have the formula:
R ¹ O— (CH ₂ CH ₂ O) _p —H
[Wherein, R ¹ and p are as defined above. ]
Is a surfactant.

Specific examples of nonionic surfactants are:
C ₁₀ H ₂₁ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₂ H ₂₅ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₆ H ₃₁ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₈ H ₃₅ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₈ H ₃₇ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₂ H ₂₅ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -C ₁₂ H ₂₅
C ₁₆ H ₃₁ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -C ₁₆ H ₃₁
C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -C ₁₂ H ₂₅
iso-C ₁₃ H ₂₇ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₀ H ₂₁ COO- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₆ H ₃₃ COO- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -C ₁₂ H ₂₅
[Wherein, p and q are as defined above. ]
Etc.

Specific examples of the nonionic surfactant, ethylene oxide and hexyl phenol, isooctanoate butylphenol, hexadecanol, oleic acid, alkane _(C 12 _{-C 16)} thiol, sorbitan mono fatty acid _(C 7 _{-C 19)} or alkyl Condensation products with (C ₁₂ -C ₁₈ ) amine and the like are included.

The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example 30 to 75% by weight, in particular 40 to 70% by weight, based on the molecular weight of the nonionic surfactant (copolymer).
The average molecular weight of the nonionic surfactant is generally 300 to 5,000, for example, 500 to 3,000.
Nonionic surfactants can be used alone or in combination of two or more.
The nonionic surfactant is preferably a combination of two or more. In a combination of two or more, at least one nonionic surfactant is R ¹ O— (CH ₂ CH) in which the R ¹ group (and / or R ³ group) is a branched alkyl group (eg, an isotridecyl group). ^{_{2 O) p - (R 2}} O) q -R 3 [ _{^{especially, R 1 O- (CH 2 CH}} 2 O) p -H] may be a compound represented by. The amount of the nonionic surfactant in which R ¹ group is a branched alkyl group is 5 to 100 parts by weight, for example, 8 to 50 parts by weight, particularly 10 parts per 100 parts by weight of the nonionic surfactant (B2). It may be up to 40 parts by weight. In a combination of two or more, the remaining nonionic surfactant is an R ¹ group (and / or R ³ group) (saturated and / or unsaturated) linear alkyl group (eg, lauryl group (n- lauryl _{^{group)) R 1 O- (CH 2}} CH 2 O) p - (R 2 O) q -R 3 [ _{^{especially, R 1 O- (CH 2 CH}} 2 O) p -H] a compound represented by It may be.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester , Polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkyl alkanolamide, acetylene glycol, oxyethylene adduct of acetylene glycol, Examples thereof include polyethylene glycol polypropylene glycol block copolymers.

  Since the dynamic surface tension of the water-based emulsion becomes low, the nonionic surfactant is preferably acetylene glycol or an oxyethylene adduct of acetylene glycol.

  Since the dynamic surface tension of the water-based emulsion becomes low (that is, the aqueous emulsion easily penetrates into the substrate), the nonionic surfactant may be acetylene alcohol (particularly acetylene glycol) or acetylene alcohol (particularly acetylene). Glycol) oxyethylene adducts are preferred.

A preferred nonionic surfactant is an alcohol having an unsaturated triple bond or an alkylene oxide adduct of the alcohol (both the alcohol and the alkylene oxide adduct are referred to as “acetylene alcohol compounds”). Particularly preferred nonionic surfactants are alkylene oxide adducts of monools or polyols having unsaturated triple bonds.
An acetylene alcohol compound is a compound containing one or more triple bonds and one or more hydroxyl groups. The acetylene alcohol compound may be a compound containing a polyoxyalkylene moiety. Examples of the polyoxyalkylene moiety include polyoxyethylene, polyoxypropylene, a random addition structure of polyoxyethylene and polyoxypropylene, and a block addition structure of polyoxyethylene and polyoxypropylene.

The acetylene alcohol compound has the formula:
HO—CR ¹¹ R ¹² —C≡C—CR ¹³ R ¹⁴ —OH, or HO—CR ¹⁵ R ¹⁶ —C≡C—H
[Wherein, each of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ is independently the same or different and is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. ]
It may be a compound shown by these. The acetylene alcohol compound may be an alkylene oxide adduct of the compound represented by this chemical formula. The alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and particularly preferably a linear or branched alkyl group having 6 to 12 carbon atoms. Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group. Moreover, as alkylene oxide, C1-C20 (especially 2-5) alkylene oxides, such as ethylene oxide and a propylene oxide, are preferable, and the addition number of alkylene oxide is preferable 1-50.

  Specific examples of the acetylene alcohol compound include acetylene diol, propargyl alcohol, 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4 , 7,9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1- Examples include pentyne-3-ol, 3-hexyne-2,5-diol, 2-butyne-1,4-diol, and the like. Polyethoxylates and ethylene oxide adducts of these specific examples are also included.

  The nonionic surfactant may not have a triple bond, or may have a triple bond. The nonionic surfactant may be only one of a nonionic surfactant having no triple bond or a nonionic surfactant having a triple bond, but a nonionic surfactant having no triple bond and a nonionic surfactant having a triple bond It may be a combination of active agents. A combination of a nonionic surfactant having no triple bond and a nonionic surfactant having a triple bond has a triple bond with a nonionic surfactant having no triple bond (eg, a nonionic surfactant having an oxyalkylene group). The weight ratio of the nonionic surfactant (for example, acetylene alcohol compound) may be 10:90 to 90:10, such as 20:80 to 80:20.

(2-3) Cationic surfactant The cationic surfactant is preferably a compound having no amide group.

Examples of cationic surfactants include amines, amine salts, quaternary ammonium salts, imidazolines and imidazolinium salts.
The cationic surfactant is preferably an amine salt, a quaternary ammonium salt, or an oxyethylene addition type ammonium salt. Specific examples of the cationic surfactant include, but are not limited to, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt type surfactants such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, Quaternary ammonium salt type surfactants such as alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like can be mentioned.

Examples of cationic surfactants are:
^{R 21 -N + (-R 22)} (- R 23) (- R 24) X -
[In the formula, each of R ²¹ , R ²² , R ²³ and R ²⁴ is independently the same or different and is a hydrogen atom or a hydrocarbon group having 1 to 50 carbon atoms;
X is an anionic group. ]
It is this compound. The hydrocarbon group may have an oxygen atom, and may be, for example, an oxyalkylene such as a polyoxyalkylene group (the alkylene has 2 to 5 carbon atoms, for example). R ²¹ , R ²² , R ²³ and R ²⁴ are preferably a hydrocarbon group having 1 to 30 carbon atoms (for example, an aliphatic hydrocarbon, an aromatic hydrocarbon or an araliphatic hydrocarbon).
Specific examples of R ²¹ , R ²² , R ²³ and R ²⁴ include an alkyl group (for example, methyl group, butyl group, stearyl group, palmityl group), aryl group (for example, phenyl group), aralkyl group (for example, benzyl group) (Phenylmethyl group), phenethyl group (phenylethyl group)).
Specific examples of X are halogen (for example, chlorine), acid (for example, inorganic acid such as hydrochloric acid, organic acid such as acetic acid (particularly fatty acid)).
The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 30 carbon atoms).

The cationic surfactant is preferably an ammonium salt, particularly a quaternary ammonium salt. The cationic surfactant has the formula:
R ³¹ _p -N ⁺ R ³² _q X ⁻
Wherein each R ³¹ is independently the same or different and is a C12 or higher (eg C ₁₂ -C ₅₀ ) linear and / or branched aliphatic (saturated and / or unsaturated) group,
Each of R ³² is independently the same or different, and is an H or C 1-4 alkyl group, benzyl group, polyoxyethylene group (number of oxyethylene groups, for example, 1 (particularly 2, particularly 3) to 50). (CH ₃ and C ₂ H ₅ are particularly preferred),
X is a halogen atom (e.g., chlorine and bromine), fatty bases C ₁ -C _4,
p is 1 or 2, q is 2 or 3, and p + q = 4. ]
It may be an ammonium salt represented by R ³¹ may have 12 to 50 carbon atoms, for example 12 to 30 carbon atoms.

  Specific examples of the cationic surfactant include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl) trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyl Di (hydropolyoxyethylene) ammonium chloride and benzyldodecyl di (hydropolyoxyethylene) ammonium chloride are included.

  Examples of amphoteric surfactants include alanines, imidazolinium betaines, amide betaines, betaine acetate, and the like. Specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethylhydroxyethyl imidazolinium betaine, lauryl dimethyl. Examples include aminoacetic acid betaine and fatty acid amidopropyldimethylaminoacetic acid betaine.

The surfactant may consist only of a surfactant compound having one or both of an amide group and an amino group, and the surfactant compound having one or both of the amide group and the amino group and other surfactants (particularly nonionic properties). A combination of surfactants). In the combination of a surfactant compound having one or both of an amide group and an amino group and another surfactant (particularly a nonionic surfactant), the surfactant compound having one or both of the amide group and the amino group and the other The weight ratio of the surfactant (particularly the nonionic surfactant) is preferably 10:90 to 90:10, such as 20:80 to 80:20, particularly 30:70 to 70:30. The amount of other surfactant other than the surfactant compound having one or both of an amide group and an amino group may be 50% by weight or less, for example, 20% by weight or less based on the total amount of the surfactant. And may be 0.1% by weight or more.
The surfactant may be a combination of two or more. Each of the surfactant compound having one or both of an amide group and an amino group, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant may be one or a combination of two or more.
The amount of the surface active compound having one or both of an amide group and an amino group may be 0.05 to 10 parts by weight, for example, 0.1 to 8 parts by weight with respect to 100 parts by weight of the polymer. The total amount of the surfactant may be 0.1 to 20 parts by weight, for example, 0.2 to 10 parts by weight with respect to 100 parts by weight of the polymer.

(3) Liquid medium The liquid medium may be water alone or a mixture of water and an organic solvent (water-miscible organic solvent). The amount of the organic solvent may be 30% by weight or less, for example, 10% by weight or less (preferably 0.1% or more) with respect to the liquid medium. The liquid medium is preferably water alone.

  The water / oil repellent composition of the present invention may contain only the non-fluorine polymer as a polymer (active ingredient), but contains a fluorine-containing polymer in addition to the non-fluorine polymer. Also good. In general, in a water / oil repellent composition (particularly, an aqueous emulsion), particles formed of a non-fluorine polymer and particles formed of a fluoropolymer exist separately. That is, it is preferable to mix the non-fluorine polymer and the fluoropolymer after separately producing the non-fluoropolymer and the fluoropolymer. Generally, a non-fluoropolymer emulsion (especially an aqueous emulsion) and a fluoropolymer emulsion (especially an aqueous emulsion) are prepared separately, and then the non-fluoropolymer emulsion and the fluoropolymer emulsion are mixed. It is preferable.

The fluorine-containing polymer is a polymer having a repeating unit derived from a fluorine-containing monomer. The fluorine-containing monomer has the general formula:
CH ₂ = C (−X) −C (= O) −Y−Z−Rf (I)
[Wherein, X represents a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.), A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, A substituted or unsubstituted phenyl group;
Y is —O— or —NH—;
Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group,
—CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ is an alkyl group having 1 to 4 carbon atoms) or
-CH ₂ CH (OZ ¹ ) CH ₂ -group (where Z ¹ is a hydrogen atom or an acetyl group) or
— (CH ₂ ) _m —SO ₂ — (CH ₂ ) _n — group or — (CH ₂ ) _m —S— (CH ₂ ) _n — group (where m is 1 to 10, n is 0 to 10, is there),
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. ]
An acrylate ester or acrylamide represented by
The number of carbon atoms in the Rf group is preferably 1-6, particularly 4-6.

The fluorine-containing polymer is a repeating polymer derived from at least one non-fluorine monomer selected from the group consisting of halogenated olefin monomers, non-fluorine non-crosslinkable monomers and non-fluorine crosslinkable monomers. You may have a unit.
The halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. Specific examples of halogenated olefin monomers are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide.

Preferred non-fluorine non-crosslinkable monomers have the formula:
CH ₂ = CA-T
[In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom);
T is a hydrogen atom, a linear or cyclic hydrocarbon group having 1 to 20 carbon atoms, or a linear or cyclic organic group having 1 to 20 carbon atoms having an ester bond. ]
It is a compound shown by these. Specific examples of non-fluorine non-crosslinkable monomers include alkyl (meth) acrylate esters, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) Acrylate, methoxypolypropylene glycol (meth) acrylate, and vinyl alkyl ether are included.

  The non-fluorine crosslinkable monomer has a compound having at least two carbon-carbon double bonds (for example, (meth) acrylic group), or has at least one carbon-carbon double bond and at least one reactive group. It may be a compound.

The weight ratio of the non-fluoropolymer to the fluoropolymer in the water / oil repellent composition is 100: 0 to 10:90, for example, 90:10 to 20:80, preferably 80:20 to 30:70. Good.
Each of the non-fluorine polymer and the fluorine-containing polymer may be a single polymer, or may be a combination of two or more polymers.
When using a combination of a non-fluorinated polymer and a fluorinated polymer, performance (particularly, water / oil repellency) equivalent to or better than when only a fluorinated polymer is used is obtained.

The polymer (non-fluorine polymer and fluoropolymer) in the present invention can be produced by any ordinary polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization. Emulsion polymerization is preferred.
If the processing agent of this invention is a water-system emulsion, the manufacturing method of a polymer will not be limited. For example, a water-based emulsion can be obtained by producing a polymer by solution polymerization and then removing the solvent and adding a surfactant and water.

  In solution polymerization, a method in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, is heated and stirred in the range of 30 to 120 ° C. for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like. Can be mentioned. The polymerization initiator is used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

  The organic solvent is inactive to the monomer and dissolves them. For example, an ester (for example, an ester having 2 to 30 carbon atoms, specifically, ethyl acetate or butyl acetate), a ketone (for example, carbon It may be a ketone having 2 to 30 (specifically, methyl ethyl ketone, diisobutyl ketone) or an alcohol (for example, an alcohol having 1 to 30 carbon atoms, specifically, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, Examples include diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in the range of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight with respect to 100 parts by weight of the total amount of monomers.

  Emulsion polymerization employs a method in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after substitution with nitrogen, the mixture is stirred and polymerized in the range of 50 to 80 ° C. for 1 to 10 hours. Polymerization initiators include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azo Water-soluble materials such as bisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide Oil-soluble ones such as t-butyl peroxypivalate and diisopropyl peroxydicarbonate are used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

  In order to obtain a polymer aqueous dispersion with excellent storage stability, the monomer is polymerized by submerging the monomer into water using an emulsifier that can impart strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. It is desirable. As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and the emulsifier is used in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomer. Preference is given to using anionic and / or nonionic and / or cationic emulsifiers. When the monomers are not completely compatible with each other, it is preferable to add a compatibilizing agent such as a water-soluble organic solvent or a low molecular weight monomer that is sufficiently compatible with these monomers. By adding a compatibilizing agent, it is possible to improve emulsifying properties and copolymerization properties.

  Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol and the like, and 1 to 50 parts by weight with respect to 100 parts by weight of water. For example, you may use in the range of 10-40 weight part. Examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., and 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of monomers, For example, you may use in the range of 10-40 weight part.

  In the polymerization, a chain transfer agent may be used. Depending on the amount of chain transfer agent used, the molecular weight of the polymer can be varied. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (for example, having 1 to 30 carbon atoms)), inorganic salts such as sodium hypophosphite and sodium bisulfite. Etc. You may use the usage-amount of a chain transfer agent in 0.01-10 weight part with respect to 100 weight part of total amounts of a monomer, for example, 0.1-5 weight part.

The treatment agent composition of the present invention may be in the form of a solution, an emulsion (particularly an aqueous dispersion) or an aerosol, but is preferably an aqueous dispersion. The treating agent composition comprises a polymer (active component of the surface treating agent) and a medium (particularly a liquid medium such as an organic solvent and / or water). The amount of the medium may be, for example, 5 to 99.9% by weight, particularly 10 to 80% by weight, based on the treatment agent composition.
In the treating agent composition, the concentration of the polymer may be 0.01 to 95% by weight, for example 5 to 50% by weight.

  The treatment agent composition of the present invention can be applied to an object to be treated by a conventionally known method. Usually, the treatment agent composition is dispersed in an organic solvent or water, diluted, and attached to the surface of an object to be treated by a known method such as dip coating, spray coating, foam coating, etc., and then dried. Taken. If necessary, curing may be carried out by applying together with a suitable crosslinking agent (for example, blocked isocyanate). Furthermore, an insect repellent, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent and the like can be added to the treatment agent composition of the present invention. The concentration of the polymer in the treatment liquid brought into contact with the substrate may be 0.01 to 10% by weight (particularly in the case of dip coating), for example 0.05 to 10% by weight.

  Examples of the object to be treated with the treating agent composition (for example, water and oil repellent) of the present invention include textile products, stone materials, filters (for example, electrostatic filters), dust masks, fuel cell components (for example, gas). Diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, plasters and the like. Various examples can be given as textile products. For example, natural animal and vegetable fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, glass fibers, and carbon fibers , Inorganic fibers such as asbestos fibers, or mixed fibers thereof.

The fiber product may be in the form of a fiber, cloth or the like.
The treatment agent composition of the present invention can also be used as an internal release agent or an external release agent.

  The polymer can be applied to a fibrous substrate (eg, a textile product, etc.) by any of the methods known for treating textile products with liquids. When the textile product is a fabric, the fabric may be immersed in the solution, or the solution may be attached or sprayed onto the fabric. The treated textile product is dried and preferably heated at, for example, 100 ° C. to 200 ° C. in order to develop oil repellency.

  Alternatively, the polymer may be applied to the textile by a cleaning method, such as a laundry application or a dry cleaning method.

  The textile products to be treated are typically fabrics, which include woven, knitted and non-woven fabrics, fabrics and carpets in clothing form, but fibers or yarns or intermediate fiber products (eg sliver or It may be a roving yarn). The textile product material may be natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or rheocell), or synthetic fibers (such as polyester, polyamide or acrylic fibers), or May be a mixture of fibers, such as a mixture of natural and synthetic fibers. The production polymer of the present invention is particularly effective in making cellulosic fibers (such as cotton or rayon) oleophobic and oleophobic. The method of the present invention also generally makes the textile product hydrophobic and water repellent.

Alternatively, the fibrous base material may be leather. In order to make the production polymer hydrophobic and oleophobic, aqueous solutions or aqueous emulsifications at various stages of leather processing, for example during the wet processing of leather or during the finishing of leather You may apply it to leather from things.
Alternatively, the fibrous substrate may be paper. The production polymer may be applied to preformed paper or may be applied at various stages of papermaking, for example during the drying period of the paper.

  “Treatment” means that a treatment agent is applied to an object to be treated by dipping, spraying, coating, or the like. By the treatment, the polymer which is an active ingredient of the treatment agent penetrates into the treatment object and / or adheres to the surface of the treatment object.

Next, the present invention will be specifically described with reference to examples and comparative examples. However, these explanations do not limit the present invention.
In the following, parts or% or ratio represents parts by weight or weight% or weight ratio unless otherwise specified.
The test procedure is as follows.

Shower water repellency test A shower water repellency test was conducted according to JIS-L-1092. The shower water repellency test was performed (as shown in Table 1 below). Represented by
Use a glass funnel with a volume of at least 250 ml and a spray nozzle that can spray 250 ml of water for 20-30 seconds. The specimen frame is a metal frame having a diameter of 15 cm. Three test piece sheets having a size of about 20 cm × 20 cm are prepared, and the sheet is fixed to the test piece holder frame so that the sheet is not wrinkled. Center the spray on the center of the sheet. Room temperature water (250 mL) is placed in a glass funnel and sprayed onto the specimen sheet (over a time period of 25-30 seconds). Remove the holding frame from the base, grab one end of the holding frame, tap the front surface down and dab the opposite end with a hard substance. Rotate the holding frame 180 ° further and repeat the same procedure to drop excess water drops. Wet specimens are compared to wet reference standards to score 0, 50, 70, 80, 90 and 100 in order of poor water repellency. Results are obtained from the average of three measurements.

Ten ending test cloths (500 mm × 205 mm) are prepared. 200 g of a test solution having a polymer concentration of 18% solids diluted to 2.0% is placed in a vat, and a total of 10 test cloths are successively processed one by one. A treatment liquid obtained by squeezing one test cloth with a mangle is collected and combined with the test liquid, and then the next one test cloth is processed. Check water repellency by shower water repellency test. As an index of continuous processability, 10 sheets having high water repellency are preferable.

Production Example 1
In a 500 ml reaction flask, 115.20 g of stearyl acrylate, 240 g of pure water, 33.0 g of tripropylene glycol, 6.08 g of dimethylaminopropylamide stearate, polyoxyethylene isotridecyl ether (EO: 18, EO represents the number of ethylene oxide units) ) 5.43 g, 1.71 g of polyoxyethylene isotridecyl ether (EO: 3) and 2.4 g of acetic acid were added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After nitrogen substitution in the reaction flask, a solution of 0.24 g of lauryl mercaptan, 0.48 g of 2,2-azobis (2-amidinopropane) dihydrochloride and 9 g of water was added and reacted at 60 ° C. for 5 hours to obtain a polymer. An aqueous dispersion was obtained. The composition of the polymer almost coincided with the composition of the charged monomer.

Production Example 2
In a 500 ml reaction flask, 115.20 g of behenyl acrylate, 240 g of pure water, 33.0 g of tripropylene glycol, 6.08 g of dimethylaminopropylamide stearate, polyoxyethylene isotridecyl ether (EO: 18. EO represents the number of ethylene oxide units) ) 5.43 g, 1.71 g of polyoxyethylene isotridecyl ether (EO: 3) and 2.4 g of acetic acid were added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After nitrogen substitution in the reaction flask, a solution of 0.24 g of lauryl mercaptan, 0.48 g of 2,2-azobis (2-amidinopropane) dihydrochloride and 9 g of water was added and reacted at 60 ° C. for 5 hours to obtain a polymer. An aqueous dispersion was obtained. The composition of the polymer almost coincided with the composition of the charged monomer.

Production Example 3
In a 500 ml reaction flask, 90.2 g of stearyl acrylate, 25.0 g of isobornyl methacrylate, 240 g of pure water, 33.0 g of tripropylene glycol, 6.08 g of dimethylaminopropylamide stearate, polyoxyethylene isotridecyl ether (EO: 18). (EO represents the number of ethylene oxide units) 5.43 g, 1.71 g of polyoxyethylene isotridecyl ether (EO: 3) and 2.4 g of acetic acid are added, and the mixture is emulsified and dispersed at 60 ° C. for 15 minutes with stirring. It was. After nitrogen substitution in the reaction flask, a solution of 0.24 g of lauryl mercaptan, 0.48 g of 2,2-azobis (2-amidinopropane) dihydrochloride and 9 g of water was added and reacted at 60 ° C. for 5 hours to obtain a polymer. An aqueous dispersion was obtained. The composition of the polymer almost coincided with the composition of the charged monomer.

Production Example 4
In a 500 ml reaction flask, CF ₃ CF ₂ — (CF ₂ CF ₂ ) _n —CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ (n = 2.0) 14.9 g, stearyl acrylate 43,46 g, pure water 110 g, Dipropylene glycol monomethyl ether 18.62g, distearyldimethylammonium chloride 3.08g, stearyltrimethylammonium chloride 0.87g, polyoxyethylene lauryl ether (EO: 18, EO represents the number of ethylene oxide units) 2.1g, polyoxy 0.65 g of ethylene isotridecyl ether (EO: 3) was added, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After the atmosphere in the reaction flask was replaced with nitrogen, a solution of 0.62 g of lauryl mercaptan, 0.31 g of 2,2-azobis (2-amidinopropane) dihydrochloride and 9 g of water was added and reacted at 60 ° C. for 5 hours to obtain a polymer. An aqueous dispersion was obtained. The composition of the polymer almost coincided with the composition of the charged monomer.

Comparative production example 1
In a 500 ml reaction flask, 115.20 g of stearyl acrylate, 240 g of pure water, 33.0 g of tripropylene glycol, polyoxyethylene isotridecyl ether (EO: 18, EO represents the number of ethylene oxide units), 8.43 g, polyoxyethylene isotri 4.71 g of decyl ether (EO: 3) was added, and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After nitrogen substitution in the reaction flask, a solution of 0.24 g of lauryl mercaptan, 0.48 g of 2,2-azobis (2-amidinopropane) dihydrochloride and 9 g of water was added and reacted at 60 ° C. for 5 hours to obtain a polymer. An aqueous dispersion was obtained. The composition of the polymer almost coincided with the composition of the charged monomer.

Example 1
After the aqueous liquid produced in Production Example 1 was diluted with pure water so that the polymer concentration was 18% solids, the ratio was 1.0%, 1.2%, 1.4%, 1.6% and A test solution (1000 g) was prepared by further diluting with water to 2.0%. In the shower water repellency test, 1.0%, 1.2%, 1.4% and 1.6% test solutions were used. A 2.0% test solution was used in the ending test. In the shower water repellency test, a sheet of PET cloth (250 mm × 205 mm) was immersed in this test solution, passed through a mangle, and treated with a pin tenter at 170 ° C. for 1 minute. Thereafter, the test cloth was subjected to a shower water repellency test. In the ending test, ten PET cloths (500 mm × 205 mm) were continuously passed through and subjected to the ending test. The results are shown in Table 2.

Example 2
After each of the aqueous liquids produced in Production Example 1 and Production Example 4 was diluted with pure water so that the polymer concentration was 18% solids, the aqueous liquids of Production Example 1 and Production Example 4 were 20 to 80 weights. Mixed in proportion. A test liquid (1000 g) was prepared by further diluting with water so that the ratio of the mixed liquid was 1.0%, 1.2%, 1.4%, 1.6% and 2.0%. Thereafter, the same treatment as in Example 1 was performed, and a shower water repellency test and an ending test were conducted. The results are shown in Table 2.

Example 3
Each of the aqueous liquids produced in Production Example 1 and Production Example 4 was diluted with pure water so that the polymer concentration was 18% solids, and then the aqueous liquids of Production Examples 1 and 4 were 47 to 53 weights. Except for mixing at a ratio, all were treated in the same manner as in Example 2, and a shower water repellency test and an ending test were conducted. The results are shown in Table 2.

Example 4
Each of the aqueous liquids produced in Production Example 2 and Production Example 4 was diluted with pure water so that the polymer concentration was 18% solids, and then the aqueous liquids of Production Example 2 and Production Example 4 were 20 to 80 weights. Except for mixing at a ratio, all were treated in the same manner as in Example 2, and a shower water repellency test and an ending test were conducted. The results are shown in Table 2.

Example 5
The aqueous liquid produced in Production Example 3 was diluted with pure water so that the polymer concentration was 18% solids, and then treated in the same manner as in Example 1 to perform a shower water repellency test and an ending test. The results are shown in Table 2.

Example 6
Each of the aqueous liquids produced in Production Example 3 and Production Example 4 was diluted with pure water so that the polymer concentration was 18% solids, and then the aqueous liquids of Production Examples 3 and 4 were 53 to 47 weights. Except for mixing at a ratio, all were treated in the same manner as in Example 2, and a shower water repellency test and an ending test were conducted. The results are shown in Table 2.

Comparative Example 1
After the aqueous liquid produced in Production Example 4 was diluted with pure water so that the polymer concentration was 18% solids, the proportion of the aqueous liquid was 1.0%, 1.2%, 1.4%, 1 A test solution (1000 g) was prepared by further diluting with water to 6% and 2.0%. Otherwise, the same treatment as in Example 1 was performed, and a shower water repellency test and an ending test were conducted. The results are shown in Table 2.

Comparative Example 2
After the aqueous liquid produced in Comparative Production Example 1 was diluted with pure water so that the polymer concentration was 18% solids, the proportion of the aqueous liquid was 1.0%, 1.2%, 1.4%, A test solution (1000 g) was prepared by further diluting with water to 1.6% and 2.0%. Otherwise, the same treatment as in Example 1 was performed, and a shower water repellency test and an ending test were conducted. The results are shown in Table 2.

Comparative Example 3
Each of the aqueous liquids produced in Comparative Production Example 1 and Production Example 4 was diluted with pure water so that the polymer concentration was 18% solids, and then the aqueous liquids of Comparative Production Example 1 and Production Example 4 were mixed in a ratio of 20 to 80. All were mixed in the same manner as in Example 1 except that they were mixed at the weight ratio, and a shower water repellency test and an ending test were conducted. The results are shown in Table 2.

  The treatment agent of the present invention can be suitably used for substrates such as textiles and masonry, and imparts excellent water and oil repellency (particularly water repellency) to the substrate.

Another aspect of the present invention is as follows.
<1>
(1) (a) 40% by weight or more of the formula:
^{_{CH 2 = CA 11 -C (=}} O) -O-A 12
[In the formula, A ¹¹ represents a hydrogen atom or a methyl group;
A ¹² is a linear or branched aliphatic hydrocarbon group having 18 to 30 carbon atoms. ]
A polymer having a repeating unit derived from a long-chain (meth) acrylate ester monomer represented by:
(2) A surfactant containing a surfactant compound having one or both of an amide group and an amino group, and (3) an aqueous emulsion treating agent comprising a liquid medium containing water.
<2>
The polymer (1) further has the formula (b):
^{_{CH 2 = CA 21 -C (=}} O) -O-A 22
[In the formula, A ²¹ represents a hydrogen atom or a methyl group;
A ²² is a linear or branched aliphatic hydrocarbon group having less than 18 carbon atoms. ]
The aqueous emulsion treating agent according to <1>, which has a repeating unit derived from a short-chain (meth) acrylate ester monomer represented by the formula (1) and has a molecular weight of less than 500,000.
<3>
The aqueous emulsion treating agent according to <1> or <2>, wherein the polymer (1) further has (c) a repeating unit derived from a non-fluorine crosslinkable monomer.
<4>
The non-fluorine crosslinkable monomer (c) is a compound having at least two ethylenically unsaturated double bonds, or a compound having at least one ethylenically unsaturated double bond and at least one reactive group <3> The aqueous emulsion treating agent according to 3>.
<5>
The polymer (1) is
(D) The aqueous emulsion treating agent according to any one of <1> to <4>, having a repeating unit derived from a halogenated olefin monomer.
<6>
The polymer (1) is
(D) The aqueous emulsion treating agent according to any one of <1> to <4>, which does not have a repeating unit derived from a halogenated olefin monomer.
<7>
The aqueous emulsion treating agent according to <5> or <6>, wherein the halogenated olefin monomer (d) is at least one selected from the group consisting of vinyl chloride and vinylidene chloride.
<8>
The aqueous emulsion treating agent according to any one of <1> to <7>, wherein the polymer (1) does not contain a fluorine atom.
<9>
In the polymer (1), with respect to 100 parts by weight of the repeating unit (a),
The amount of the repeating unit (b) is 0 to 150 parts by weight,
The amount of the repeating unit (c) is 0 to 50 parts by weight,
The aqueous emulsion treating agent according to any one of <1> to <8>, wherein the amount of the repeating unit (d) is 0 to 100 parts by weight.
<10>
A surface active compound having one or both of an amide group and an amino group has the formula:
^{R 11 -C (= O) (} R 12 -) N- (CH 2) n -N (-R 13) (- R 14)
[In the formula, each of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is independently the same or different and is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and n is 0 to 10. ]
The aqueous emulsion treating agent according to any one of <1> to <9>, which is a compound represented by:
<11>
The aqueous emulsion treating agent according to any one of <1> to <10>, wherein the surfactant (2) further contains a nonionic surfactant.
<12>
Nonionic surfactant has the formula:
_{^{R 1 O- (CH 2 CH 2}} O) p - (R 2 O) q -R 3
[Wherein, R ¹ is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an acyl group, and each R ² is independently the same or different and has 3 or more carbon atoms (for example, 3 To 10), R ³ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, and q is 0 or a number of 1 or more. . ]
The aqueous emulsion treating agent according to <11>, which is a compound represented by the formula:
<13>
<11> The aqueous emulsion treating agent according to <11>, wherein the nonionic surfactant is an acetylene alcohol compound selected from the group consisting of acetylene alcohol and an oxyethylene adduct of acetylene alcohol.
<14>
The acetylene alcohol compound has the formula:
HO—CR ¹¹ R ¹² —C≡C—CR ¹³ R ¹⁴ —OH, or HO—CR ¹⁵ R ¹⁶ —C≡C—H
[Wherein, each of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ is independently the same or different and is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. ]
The aqueous emulsion treating agent according to <13>, which is a compound represented by the formula:
<15>
The aqueous emulsion treating agent according to any one of <1> to <14>, wherein the surfactant (2) further contains a cationic surfactant.
<16>
The cationic surfactant has the formula:
^{R 21 -N + (-R 22)} (- R 23) (- R 24) X -
[In the formula, each of R ²¹ , R ²² , R ²³ and R ²⁴ is independently the same or different and is a hydrocarbon group having 1 to 30 carbon atoms,
X is an anionic group. ]
The aqueous emulsion treating agent according to <15>, which is a compound represented by the formula:
<17>
The aqueous emulsion treating agent according to any one of <1> to <16>, wherein the fiber treating agent further contains a fluoropolymer.
<18>
The aqueous emulsion treatment agent according to any one of <1> to <17>, wherein the dynamic surface tension of the aqueous emulsion is 55 mN / m or less.
<19>
The aqueous emulsion treatment agent according to any one of <1> to <18>, which is a fiber treatment agent.
<20>
The aqueous emulsion treating agent according to any one of <1> to <19>, which is a water / oil repellent or an antifouling agent.
<21>
A method for treating a textile product, comprising treating the textile product with the aqueous emulsion treating agent according to any one of <1> to <20>.
<22>
<1>-<20> The textiles processed with the water-system emulsion processing agent in any one of.

Claims (7)

(1) (a) Formula:
^{_{CH 2 = CA 11 -C (=}} O) -O-A 12
[In the formula, A ¹¹ represents a hydrogen atom or a methyl group;
A ¹² is a linear or branched aliphatic hydrocarbon group having 18 to 30 carbon atoms. ]
A non-fluorine polymer having a repeating unit derived from a long-chain (meth) acrylate ester monomer represented by:
(2) A surface treatment agent comprising a surfactant containing a surface active compound having one or both of an amide group and an amino group, and (3) an aqueous emulsion containing a liquid medium containing water ,
A surface treatment agent in which the surface treatment agent contains a fluoropolymer .   The surface treating agent according to claim 1, wherein the non-fluoropolymer (1) has a repeating unit derived from a (meth) acrylate monomer having a cyclic hydrocarbon group. A surface active compound having one or both of an amide group and an amino group has the formula:

[In the formula, each of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is independently the same or different and is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and n is 0 to 10. ]
The surface treatment agent according to claim 1, which is a compound represented by the formula: Surfactant (2) further comprises one or both of a nonionic surfactant and a cationic surfactant,
The nonionic surfactant is at least one selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides;
The surface treating agent according to any one of claims 1 to 3, wherein the cationic surfactant is at least one selected from the group consisting of an amine, an amine salt, a quaternary ammonium salt, an imidazoline and an imidazolinium salt. The surface treating agent according to any one of claims 1 to 4 , which is a water / oil repellent or an antifouling agent. Comprising the step of treating said textile with a surface treating agent according to any one of claims 1 to 5, a method of processing a textile product. A textile product treated with the surface treatment agent according to any one of claims 1 to 5 .